Fiber reactive and fiber non-reactive fluoro-alkylacetals of dialdehydes and materials treated therewith



United States Patent 3,535,247 FIBER REACTIVE AND FIBER NON-REACTIVEFLUORO-ALKYLACETALS 0F DIALDEHYDES AND MATERTALS TREATED THEREWITHDomenick Donald Gagliardi, 185 Howland Road, East Greenwich, RI. 02818No Drawing. Continuation of application Ser. No.

583,429, Sept. 30, 1966, which is a continuation-inpart of applicationSer. No. 295,507, July 16, 1963. This application July 7, 1969, Ser. No.845,641 Int. Cl. Ctl7c 43/30 U.S. Cl. 260-65 8 Claims ABSTRACT OF THEDISCLOSURE Perfiuro diacetals of dialdehydes are provided which areuseful for treating substrates in order to obtain oil and waterrepellent finishes thereon. Of the four ether groups present in themolecule at least one contains a C to C alkyl having a terminal CHF orCF grouping and wherein at least 70% of the normally present hydrogenatoms of the alkyl have been replaced by fluorine atoms. The remainingether groups may be either similar or different perfluoro alkyl moietiesof 3 to 22 carbon atoms or alkyl of 1 to carbon atoms. Where two of theether groupings on the same carbon atom are alkyl of 1 to 4 carbonatoms, the compounds are reactive with substrates containing activehydrogen therein, e.g. cellulose. The diacetals of this invention areeither liquids or high-melting waxes depending upon the molecular weightof the product.

This application is a continuation of application S.N. 583,429, filedSept. 30, 1966 and now abandoned which is in turn a continuation-in-partof application SN. 295,507, filed July 16, 1963.

The present invention relates to the preparation of fiber reactive andnon-reactive fluoroalkylacetals of di aldehydes and to textile materialsand other substrates to which said fluoroalkylacetals are affixed.

The treatment of textile materials to endow the textile with an abilityto shed water or repel water dates from at least the early nineteenthcentury when Macintosh presented to the world his treated cloth having asufficient water-repellency that his name was used to designate a groupof garments known as Macintoshes. From the time of Macintosh to 1935 to1940 textile materials were coated with various compositions such asrubber, linseed oil-rubber mixtures, synthetic dopes, and otherwhimsically strange compositions which formed a continuous coating onthe woven material and prevented the penetration of water.

Without understanding the basic principles of surface free energy,contact angle and spreading coefficient several unrelated practicaldevelopments emerged during the years 1935 to 1940 which changed the artof textile waterproofing. In Germany, especially at Chemische FabrikePfereze, a series of parafiin wax emulsions was developed which, whenpadded onto textiles, produced a high contact angle of water drops onthe treated surface and a high degree of shower resistance withoutchanging the porosity or air-permeability of the textile material. Thetreated fabrics were not wetted by water or water-borne liquids andstains because of the change in free energy of the surfaces of the fiberand not be cause of closing or plugging the interstices of the fabric.

By use of the new wax emulsion-metallic salts compositions, it was thenpossible to produce fabrics which were water repellent and had the feeland appearance of conventional textiles but did not look like oil-clothsice or rubberized coated fabrics. The only practical limitation of suchcompositions was the durability to washing and dry cleaning. Such waxemulsion-metallic salts compositions usually contain (1) paraflin wax ormixtures of vegetable wax esters such as carnauba, candelilla, or sugarcane wax; (2) an emulsifying agent, generally glue, gelatin and rosinsoaps; and (3) an aluminum or Zirconium salt usually the formate oracetate. The primary function of the salts is to insolubilize the glueand other emulisfiers after the emulsion is deposited on the fibers.

A large variety of such products are still used as lowcost, non-durablewater repellents for textiles. Other than water repellency for rainwearfabrics, such compositions produce fabrics which have a fair degree ofspotand stain-repellency against water-borne stains.

The search for durable or permanent water repellents, especially forcellulosic fibers, was initiated by the deficiencies of the previouslydiscussed wax emulsion-metallic salt products.

The first important development was the use of octodecyloxymethylpyridinium-chloride available in England under the trade name Velan.Velan is a quaternary ammonium compound made by the chloromethylation ofoctadecanol followed by quaternization with pyridine to yield acomposition corresponding to the formula:

CISTIKIO CHQN C This structure, unlike other quaternaries, is unstableand under acid conditions reacts with surfaces containing activehydrogen, e.g., the hydrogen of the hydroxyl group of cellulose fibers.This, if Z is the base of the cellulose molecule then the reaction maybe represented by the equation Fabrics treated with such a compound aredurably Water repellent, are porous, soft, and appear like untreatedfabrics. A major improvement in this product was made by du Font andWarwick Chemical Company, who produced the stearamidomethyl analog ofVelan having a composition corresponding to the formulaCl7l'I3500NIICI'I2N O known commercially as Zelan and Norane R. Theadvantages of the stearamide product is its greater initial waterrepellency and greater durability to washing. Such products are still inthe forefront of the leaders in rainwear fabrics finishes.

The search for fiber reactive or durable water-repellent textilefinishes continues. Other classes of water-repellent textile finisheshave been introduced to the textile finishing art of which siliconewater-repellents methylolstearamide compositions (Pernielj Ahcovel NW),hydrophobic resins (Norane GG, Ranedare R, Argus DWR), octadecylketenedimer (Aquapel) and others are representative.

While durable water repellents, such as those briefly mentionedhereinbefore, had been initially designed for outerwear and raincoattype applications, in the period from 1950 to 1956 the use of suchproducts as finishes for mens suitings, dress goods, and upholsterymaterials become almost common place. In these uses, promotionalemphasis was placed not upon water-repellency but upon resistance tospotting and staining. It was subsequently observed that fabrics treatedwith such water-repellents had a high degree of resistance to soiling bywater-borne soils and strains and were easier to launder. The onlylimitation of such finishes was that they appeared to attract oily soilsand the fabrics treated with these finishes were not stain repellentagainst oily materials such as oils, greases, gravy, mayonnaise, and thelike.

While resistance to soiling by water-borne soils and stains, e.g.,coffee is of considerable importance, the development of finishes whichresist staining by oil-borne stains such as mayonnaise and, particularlyfinishes which do not attract oily particulate-soil open-up an entirelynew field of textile finishing. For example, the cocktail party and thecanapes served therewith does not concomitantly include the need to dryclean the rugs. Of even greater importance, is the ability of a finishto shed rather than attract oily particulate-soil. The incidence ofstaining a shirt-front with mayonnaise is only once or twice a day butthe dust, i.e., particulate-soil of the environment and the oilyexudations of the human skin which deposit on the neckband and wrist-endof the cuffs of mens shirts is always present during each minute of thehours during which the shirt is worn. Thus, it is manifest that, whilethe disadvantage of these durable waterrepellents when used as finishesfor mens suitings, dress goods, upholstery and the like may not seem tooimportant upon cursory consideration, after more profound review theboon of finishes which repel not only oil-borne stains but in additionrepel rather than attract oily particulate-soil becomes self-evident.Such particulate-soil repellent finishes are provided by the presentnovel perfiuoroalkylacetals of dialdehydes of the present invention.

The novel perfiuoroalkylacetals of dialdehydes of the present inventionprovide finishes for textile materials of two relatively durableclasses, i.e., one class of the present perfluoroalkyl acetals isnon-reactive with the fiber, the other class of the presentperfiuoroalkylacetals is reactive with active hydrogen contained in thesurface of the fiber.

NON-REACTIVE PERFLUOROACETALS The perfiuoroalkylacetals of the presentinvention which are non-reactive with the fiber have compositionscorresponding to the formula omoHanofi Q02 OQ3 I Where Q is the residueof an alcohol having 3 to 22 carbon atoms, having either a terminal -CHFgroup or, preferably, a terminal --CF group in which at least 70 percentof the hydrogen atoms of the alkyl group of the parent alcohol arereplaced with fluorine atoms and the alkyl chain is straight or branchedand n is zero to 22, and the other Qs are similar to Q or an aliphaticchain containing at least 6 uninterrupted carbon atoms, and preferablyalkyl of 6 to 30 carbon atoms.

REACTIVE PERFLUOROACETALS The perfiuoroacetals of the present inventionwhich are reactive with active hydrogen contained in the surface of thefiber have compositions corresponding to the formula Z Y II where Q andn have the significance given hereinbefore, X and Y together mayrepresent =0 (i.e., an aldehyde) or may be independently OR wherein R isalkyl of 1 to 4 carbons, and Z may be OQ1, 0R or CR where R is analiphatic chain containing at least 5 uninterrupted carbon atoms. Thesefiber-reactive-perfiuoroacetals react with the active hydrogen containedin the surface in a manner corresponding to that indicated by thefollowing equation in which Z(OI-I) represents cellulose having inactive hydrogen atoms in the surface no 0 ntonano mo (gnaw-L mo n Theperfiuoroalkylacetals of dialdchydes of the present invention are eitherliquids or high melting waxes depending on the value of (n) and on thechain length of the fiuoroalcohol (Q OH).

The preparation of dialdhyde diacetals is described in US. Pat. No.2,556,312. The patentee discloses that the initial overall reactionbetween an orthoformic ester and open chain alkenyl alkyl ether is adiacetal of malondialdehyde having a structure illustrated by thefollowing formula RO OR III R0 OR OHCR INOE RO OR IV wherein at leastone of the Rs is lower alkyl, e.g., methyl, ethyl, isopropyl, n-propyl,isobutyl, n-butyl and the others independently among alkyl, e.g., C to Cand R and R are as indicated above in Formula III.

Specific acetals as illustrative only of Formula IV include:

, ,2,2-tetraethoxyethane ,3,3-tetraethoxypropane ,4,4-tetraethoxybutane,5,5-tetraethoxypentane ,2,2-tetraisopropoxyethane,6,6-tetraisopropoxyhexane ,l0,IO-tetraisopropoxydecanel2,12-tetraisopropoxydodecane ,16,16-tetraisopropoxyhexadecane,20,20-tetraisopropoxyeicosane ,20,20-tetraethoxyeicosane-diethoxy-2,Z-diisopropoxyethane -diethoxy-2,2-di-decyloxyethane-diethoxy-2,Z-di-dodecyloxybutane 1,1-diethoxy-2,2-di-n-butoxydecane 1,1,2-triethoxy-Z-decyloxyethane l-ethoxy-l,2,2-tri-dodecyloxyethane1,1-tetraethoxy-4,4-di-n-octyloxybutane1,1-tetraethoxy-3,3-di(hexyloxyhexyloxy)pentane The followingfluoroalcohols are illustrative of those Q OH compounds which arecontemplated herein:

. 1H,1H,3H-periluoro-1-octanol The preparation of tetra-acetals ofglyoxal is described in US. Pat. No. 2,360,957. This patentee statesthat glyoxal tetra-acetals are prepared in economic yields by directreaction at elevated temperatures of glyoxal with a lower, chloroalkanolto produce the tetra-acetals having a composition represented by theformula In US. Pat. No. 2,681,370 the preparation ofperfluoroalkylaldehydealkylhemiacetals having the generic formu la ORClin which each n is an integer from 1 to 12, by direct photochlorinationof alcohols having the general formula H(CF CF CI-IOH, in which n hasthe same meaning as before, at temperatures of from C. to 80 C. usingfrom 0.1 to 0.5 mol of chlorine per mol of alcohol.

The dialdehyde diacetals described in U.S. Pat. No. 2,556,312 are saidto be useful as pharmaceutical intermediates. The tetra-acetals ofglyoxal described in U.S. Pat. No. 2,360,957 are said to possess meritas an addition agent for extreme pressure lubricants, in makingrubber-like products by condensation with polysulfide compounds, and itsplurality of chlorine atoms makes it a valuable intermediate for thesynthesis of many compounds of unusual structure and properties.

The only use suggested for the perfluoroalkylaldehyde alkylhemiacetalsin US. Pat. No. 2,681,370 is a commercially valuable way of transportingthe corresponding fluorocarbon aldehyde compounds in pure form.

The fluorinated hemiacetals described in US. Pat. No.

2,842,601 are said to be readily converted to the correspondingaldehydes and this makes them valuable as a convenient storage source ofaldehydes.

It is also stated that, by chlorination, theomega-chloroomega'-hydroperfluoro aliphatic hydrocarbons are pro ducedwhich are known to be useful as intermediates in the preparation ofsurface active agents and treating agents for paper, textiles, and thelike and highly fluorinated compounds useful as heat transfer media andthe like as described in US. Pats. Nos. 2,790,815 and 2,551,573.

It will be observed that none of the disclosures of the US. patentsdiscussed briefly hereinbefore have any discussion of endowing textilematerials with the capability to repel rather than attractparticulate-soil.

Yet, as emphasized hereinbefore, probably the most importantcharacteristic of a finish for textile materials such as dress goods,mens suitings, floor coverings, upholstery, and the like is thecapability to repel rather than attract particulate-soil.

The perfiuoroalkylacetals of dialdehydes can be applied from aqueousemulsions thereof or from solutions thereof in organic solvent. Thefabric to which the acetal is to be afiixed is contacted with theaqueous emulsion or the solution of the acetal to at least eighty toninety percent wet pick-up of a solution containing at least one percentsolids. Generally below about 0.8% by weight perfluoro compound based onthe weight of the fabric does not give optimum results although aslittle as 0.1% is effective. Up to 10% by weight may be used butpreferably not more than about 5% gives maximum benefits. The treatedfabric is then cured at a temperature in the range of from roomtemperature to about 375 F. for a period of time, e.g., five to tenminutes at 300 F.

The perfiuoroalkanols, having a terminal CF H or a terminal CF group canbe reacted with other polyaldehydes such as polyaldehyde starch,condensed acrolein aldehyde. The novel perfluoroalkylketals can beprepared by transetherification of methyl, ethyl, or propyl ketals ofthe polyaldehydes of starch, condensed acrolein and the like or bydirect reaction of the perfiuoroalkanol and the polyaldehyde.

EXAMPLE 1 Illustrative of the capability of the fluoroalkylacetals ofdialdehydes to endow textile materials to which the fluoroalkylacetalsare aflixed with capability to shed particulate soil and to repelwaterand oil-borne stains are the data presented in Table I.

Exemplary of the perfluoroalkylacetals of dialdehydes is that preparedfrom trihydrohonafluoroalcohol [H (C1 CH OH see US. Pat. 2,917,409,Example 1] and malonalde- B.Bcfore washing as described hereinafter.A.Atter washing as described hereinafter.

EXAMPLE 2 Example 1 is repeated using the following acetals indimethylformamide at the indicated concentrations and drying at roomtemperature.

Conc. Reference to Formula I Q1 and QF 2)6 z-; Q3 and Q4 lauryl and 11:0

B. 1% Q and Q H(CF CH Q and Q isooctyl and n=1 In all instancesexcellent oil repelleney and soil resistance comparable to Example 1 areobtained. The treated textiles also are characterized by goodwater-repellent properties.

EXAMPLE 3 Example 2 is repeated except that the treated textiles arecured for 5 minutes at 300 F. Similar results are obtained.

EXAMPLE 4 Example 2 is repeated using the following compounds:

Cone. Reference to Formula II A. 1% Q and Z F(CF CH X and Y together areand 11:0

B. 1% Q1 and Z F(CF CH X and Y together are 0) and 11:1

C, 1% Q and Z F(CF CH X and Y:ethyl and 11:0

D. 1% Q and #F(CF CH X and Y:iso-

propyl and 11:1

E. 3% Q and Z=F(CF CH X:ethyl; Y:

lauryl and 11:0

F. 3% Q=H(CF CH Z:decyl; X and Y:

ethyl and 11:0

G. 4% Q=H(CF CH Z:octyl; X and Y together are 0) and 11:0

H. Q and X and Y:ethyl and 11:0

and Y together are (=0) and 11:0

Illustrative of the preparation of the perfiuoroalkylacetals ofdialdehydes is that of the C trihydrofluoroacetal of tetraethoxypropane.Sixty-four grams of C trihydrofluoroalcohol [F I-IC(CF CH OH], about0.12 mol, were reacted with seven grams of tetraethoxypropane (C H O) CH about 0.032 mol, dissolved in fifty grams of dimethylformamide and 1.0gram of concentrated sulfuric acid. The mixture was held at 100 C. fortwo hours, then the ethanol produced and unreacted ethoxypropane wereremoved under a vacuum. Thereafter at a higher temperaturedimethylformamide 3% ClCHzCllzCHzCHzCHzO ClClIzOHzCHzOHgOHzO was removedby distillation under a vacuum. A residue of 67.3 grams of a waxy solid.

where Q is the perfiuoroalkyl radical of the C trihydrofiuoroaleohol, FCH(CF CH were obtained.

The foregoing reaction is illustrative of the preparation of theperfluoroalkylacetals of dialdehydes by transetherification. However,these perfluoroalkylacetals of dialdehydes can also be made by directreaction of the perfluoroalkanol and a dialdehyde.

EXAMPLE 5 Employing the compounds and concentrations described inExample 2, dispersions are prepared using 0.5% sodium lauryl sulfate asthe emulsifier. Concentrated solutions of compounds in dimethylformamideare emulsified in water with the aforementioned emulsifying agent. Theseemulsions are then applied and dried at room temperature. Excellent soiland Water-proofing is obtained. Illustrative of the water-proofingcharacteristics, the textiles treated with compound 2D has a sprayrating of (as hereinafter described). Compounds 2F, 2H, 2] and 2M alsogive 100 ratings.

EXAMPLE 6 Example 1 is repeated except that in place of thefluoroalcohol used there, 2 mols of trifluoroethanol are used. Textilestreated with this reaction product exhibit no oil or Water-repellencyand no soil resistance.

EXAMPLE 7 The procedures of Examples 2 and 3 are repeated using thefollowing acetals in the indicated concentrations.

A. 1% n-hexyl-O O -u-hexy1 C H C H n-hexyl-O O -n-hcxyl B. 5% 2-etl1ylhexyl-O O-Z-ethyl hcxyl C II C H 2-otl1yl hoxyl-O 0-2-ethyl llcxyl C. 3%n-hexyl-O 0 C 2115 C H-C II n-hoxyl-O O C2115 D; 1% 0211 0 0 C2H5 C H 0I11 C 11 E. 3% (llCallit) OCzIltUl C 11 (J H2 C II ClC21I4O OCzIIiCl Inno case do the treated textiles exhibit any oil or soil repellency astested herein or any noticeable waterrepellency.

EMMPLE 8 An emulsion is prepared as follows:

2g. of normal-no oonnoFmF CI-I(CH2)22CH mornaorno oar-moron is dissolvedin 10 g. of dimethylformamide and then the solution is added to asolution (120 F.) of 1 g. of a non-ionic surfactant (dinonyl phenol +10ethylene oxide condensate) in 100 g. water while Stirring vigorously.Separate swatches of a cotton textile, an acetate textile, a nylontextile, a Dacron textile, and a wool textile are treated with theaforementioned emulsion and the swatches are dried at room temperature.All of the materials exhibit excellent oil-, soiland water-repellency.

The particulate-soil repellency of the textile materials to which thenon-reactive or reactive perfiuoroalkylketals of polyaldehydes have beenafiixed is determined by a particulate-soil repellency test. A syntheticsoil is used to determine the efficacy of a finish. The recommendedcomposition of this synthetic oily particulate soil is given below:

Ingredient: Percent by weight Peat moss 38 Cement 17 Kaolin clay 1 17Silica, 200 mesh 2 17 Furnace black 3 1.75 Red iron oxide 4 0.50 Mineraloil 8.75

R. T. Vanderbi1tPeer1ess Davidson Chemical 00.

== Benny & Smith Co.Mo1iacco 4 C. K. Williams Co.

The dry ingredients are blended thoroughly, dried in a forced draftconvection oven for eight hours at 50 C., milled twenty-five hours withceramic balls, and stored in a polyethylene bag.

GRC PARTICULATE SOIL TEST Fifteen to twenty 6" x 8" numbered specimens(usually 80 x 80 cotton) including at least one untreated control aretumbled for thirty minutes with 10 percent of the aforedescribed oilyparticulate soil based on the weight of the fabric. The tumbling iscarried out in a liter capacity Five Minute Homer Cleaner at 44 r.p.m.Six No. 8 Neoprene rubber stoppers are distributed among the specimensto increase the mechanical action. At the end of the tumbling, thespecimens are removed and each shaken up and down fifteen times by handto remove surface dirt, i.e., loosely adherent or non-adherent dirt.

The specimens are then cut in two to provide two 4" x 3 pieces. One-halfis washed with 50 grams of Fab in a cotton cycle with a S-pound dummyload, hung to dry, and lightly ironed under a clean cloth.

The degree of soiling is determined with the Photovolt Reflectance Meter(Iri Blue Filter). The arithmetic average of six reflectance readings isreported as the reflectance of the specimen. The higher the reflectancethe less particulate-soil has adhered to the specimen.

Water repellency-Resistance to Wetting (Spray Test), AATCC Standard. Test Method 22-1952: This test method is applicable to any textilefabric. It measures the resistance of fabrics to wetting by a Waterspray and the results depend primarily on the degree of hydrophobicityinherent in the fibers and subsequent treatments applied. Water issprayed against the taut surface of a test specimen. Evaluation of thewetted pattern is readily made by comparing the wetted pattern withstandard wetting pattern picture: 100No sticking or wetting of the uppersurface.

Slight random sticking or wetting of the upper surface.

80Wetting of the upper surface at spray points.

7 0-Partial wetting of the whole of the upper surface.

50Complete wetting of the whole of the upper surface.

0Complete wetting of the whole of the upper and the lower surfaces.

The test specimen, fastened securely and wrinkle-free in a metal hoophaving a diameter of about 6 inches is placed and centered 6 inchesunder a standard spray nozzle at an angle of 45 degrees to thehorizontal. Two hundred and fifty milliliters of water at 80 2 F. ispoured into a funnel attached above the spray nozzle. The spray laststwenty-five to thirty seconds at the end of which time the hoop is takenby one edge and the opposite edge tapped smartly once against a solidobject with the wet side facing the solid; this procedure is repeatedwith the hoop reversed 180 degrees.

Oil repellency-3M Oil Repellency Test: 3M Textile Chemicals Appendix ATest Methods, page 1: This Minnesota Mining and Manufacturing oilrepellency test is based on the different penetrating properties of twohydrocarbon liquids, mineral, e.g. Nujol a liquid paraffin having adensity in the range of 0.83 to 0.905, and nheptane. The Nujol-heptaneproportions for each rating Were selected by 3M to give oily stainresistance somewhat comparable to the water-borne stain resistancecorresponding to each of the spray ratings of the AATCC Standard TestMethod 22-1952.

Percent heptane Percent Nujol Oil repellency rating by volume by volume1 No hold out of Nujol.

The standard oil-heptane mixtures are contained in small stopperedmedicine dropper bottles. A drop of each mixture is placed on the fabricto be tested. The appearance of the test oil is observed through thedrop. Note is made Whether wetting or penetration occurs. The numbercorresponding to that mixture containing the highest percentage ofheptane which does not penetrate or wet the fabric after three minutesis considered the oil repellency rating of the system. V

The change in the optical refractivity of the drop is often anindication of wetting. In some cases wetting can be better determined byobserving the other side of the fabric. In reporting oil/heptane ratingthe symbol 0+ is indicative of a modicum of resistance to wetting byoil.

From the foregoing those skilled in the art will recognize that theforegoing discussion has provided a description of novelperfluoroalkylketals and perfluoroalkylhemiketals of polyaldehydeshaving at least two aldehyde groups. In addition, there is provided adescription of the improved resistance to soiling by particulate-soilimparted to textile materials such as dress goods, mens suitings, floorcoverings, and the like by these perfluoroalkylketals reactive with ornon-reactive with active hydrogen contained in the surface of thetextile fiber.

I claim: 1. Compounds of the formulae:

l 3 CH(CH2)nCH Q2 Q4 and II. Q10 0R1 /0H(0H2)..OE Z 0R1 (1) wherein Q isan alkyl group of from 3 to 22, said alkyl having a terminal groupselected from the group consisting of CHF and -CF and said alkyl havingat least 70 percent of the hydrogen atoms thereof replaced by fluorineatoms,

(2) Q Q and Q; are independently selected from the group consisting of Qfluoroalkyls and alkyl of 6 to 30 carbon atoms,

(3) the Rfs are independently alkyl of 1 to 4 carbon atoms,

(4) Z is selected from the group consisting of OQ and alkoxy of 1 to 30carbon atoms, and

(5) n has a value of from 0 to 22.

2. Compounds as defined in claim 1 of Formula I.

3. Compounds as defined in claim 1 of Formula II.

4. Compounds as defined in claim 2 wherein Q Q and Q; are Qfluoroalkyls.

5. Compounds as defined in claim 2 wherein Q is a Q fiuoroalkyl and Qand Q; are alkyl.

6. Compounds as defined in claim 3 wherein Z is OQ 1 2 7. Compounds asdefined in claim 3 wherein Z is alkoxy of 1 to 4 carbon atoms.

8. Compounds as defined in claim 3 wherein Z is alkoxy of 5 to 30 carbonatoms.

References Cited UNITED STATES PATENTS HOWARD T. MARS, Primary ExaminerU.S. Cl. X.R.

